Intermolecular Oxidative Addition of Aryl Halides to Platinum(II) Alkyl Complexes

We report a well-defined example of intermolecular aryl halide oxidative addition (OA) to Pt­(II). Complexes of the type (IMes)­PtMe2(L) and (IMes′)­PtMe­(L) (L = SMe2, pyridine; IMes = N,N-bis­(2,4,6-trimethylphenyl)­imidazol-2-ylidene; IMes′ = cyclometalated IMes) undergo intermolecular OA of phenyl iodide (PhI) at 60 °C, producing toluene via reductive elimination from a proposed Pt­(IV) phenyl species. Isolation of a model Pt­(IV) OA product provides evidence for a Pt­(II)/Pt­(IV) pathway. The OA of PhI is not limited to Pt­(II) IMes complexes; analogous reactions also proceed with phosphine-ligated Pt­(II) dialkyl complexes, demonstrating that this reaction is feasible for a variety of electron-rich Pt­(II) complexes bearing labile ligands.